JPH0616177B2 - Photoconductive member for electrophotography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to light (herein, light in a broad sense, that is, ultraviolet light,
Visible light, infrared light, X-rays, γ-rays, etc.).

As a photoconductive material for forming a photoconductive layer in an image forming member for electrophotography in an image forming field or an image reading field in a solid-state imaging device, it has a high sensitivity and an SN ratio (photocurrent (Ip) / (I
d)) is high, has absorption spectrum characteristics that match the spectrum characteristics of electromagnetic waves to be irradiated, has high photoresponsiveness, has a desired dark resistance value, and is non-polluting to the human body during use, Furthermore, the solid-state image pickup device is required to have characteristics such that an afterimage can be easily processed within a predetermined time. Particularly, in the case of an electrophotographic image forming member incorporated in an electrophotographic apparatus used as an office machine in an office, the pollution-free property at the time of use is an important point.

Based on this point of view, amorphous silicon (hereinafter referred to as a-Si) is used as a photoconductive material that has been receiving attention recently.
For example, German Laid-Open Publication Nos. 27469667 and 2855518 apply to electrophotographic image forming members, and German Laid-Open Publication No. 2933411 applies to photoelectric conversion reading devices. Each is listed.

However, a conventional photoconductive member having a photoconductive layer made of a-Si is used in an environment such as dark resistance value, photosensitivity, photoresponsiveness, and other electrical, optical, and photoconductive characteristics and humidity resistance. In the actual situation, it is necessary to further improve the characteristics in terms of characteristics and stability over time.

For example, when a-Si is applied to an image forming member for electrophotography, if high photosensitivity and high dark resistance are measured, afterimages due to residual potential, so-called ghost phenomenon occurs when repeatedly used for a long time, The surface of the photoconductive layer is corona charged,
Since it is constantly exposed to harsh chemical and physical conditions such as rubbing with toner and paper, cleaning with a blade, and the like, its change with time sometimes causes a fatal image defect.

Furthermore, when the photoconductive layer is made of an a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type are used. A boron atom, a phosphorus atom, or the like for control, or other atoms for improving other characteristics are contained in the photoconductive layer as constituent atoms, respectively, depending on the content of these constituent atoms. There may be a problem in the electrical and photoconductive properties of the formed layer.

Particularly in the outermost layer region of the photoconductive layer, dangling bonds are likely to be formed in the manufacturing process depending on the content and distribution of the contained atoms. For this reason, problems of variously changing behaviors of charges and structural stability are particularly important. Whether or not the photoconductive member exhibits the intended function is often determined by the number of dangling bonds in the layer region on the outermost surface of the photoconductive layer.

When the electrophotographic image forming member is produced by a generally known method, for example, the life of a photocarrier generated by light irradiation in the formed photoconductive layer is not sufficient in that layer, which is sufficient. If the image density cannot be obtained or the image exposure amount is large, excess photocarriers generated in the vicinity of the surface of the photoconductive layer flow laterally, and further, the injection of charges from the support side is sufficiently blocked. In many cases, problems such as the image being liable to become unclear often occur.

Therefore, when the photoconductive member is made of an a-Si material, the photoconductive layer having the above-mentioned electrical and optical characteristics and the surface protective layer which is chemically and physically stable while maintaining these characteristics. Is required, and such a layer structure makes it possible to obtain a high-quality image for a long time.

The present invention has been made in view of the above points, and from the viewpoint of applicability and applicability of a-Si as a photoconductive member used in an image forming member for electrophotography, a solid-state imaging device, a reader, and the like. As a result of continuing intensive and comprehensive research and study, an amorphous material containing a silicon atom as a matrix and at least one of a hydrogen atom (H) and a halogen atom (X), that is, so-called hydrogenated a-Si, halogenated A layer structure of a photoconductive member having a photoconductive layer composed of a-Si or halogen-containing hydrogenated a-Si (hereinafter collectively referred to as a-Si (H, X)) The photoconductive member designed to be specified to not only exhibit extremely excellent characteristics in practical use, but also surpasses in all respects in comparison with conventional photoconductive members, in particular, As a photoconductive member for electrophotography Is based on the point found to have significantly better properties.

The present invention provides a photoconductive member for electrophotography, which has a high density, produces a clear halftone, has a high resolution, and can easily obtain a high-quality image without image defects and image deletion. To aim.

Another object of the present invention is an all-environmental type in which electrical, optical, and photoconductive properties are almost always stable without being affected by the use environment, and the light fatigue resistance is remarkably long and in repeated use. It is also an object of the present invention to provide a photoconductive member that does not cause a deterioration phenomenon, has excellent durability, and has no or almost no residual potential observed.

Another object of the present invention is that when applied as an electrophotographic image forming member, it has a sufficient charge retention ability during a charging process for electrostatic image formation, and a normal electrophotographic method is extremely effectively applied. To provide a photoconductive member having excellent electrophotographic properties that can be achieved.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity, high SN ratio characteristics and good electrical contact between laminated layers.

That is, the photoconductive member for electrophotography of the first invention of the present invention is a photoconductive layer, a surface layer, which comprises a support, silicon as a matrix, and at least one of a hydrogen atom and a halogen atom as a constituent atom. A photoreceptive layer formed on the support, and at least 20Å from the free surface side of the photoreceptive layer.
The spin concentration measured by ESR in the surface layer region at the layer thickness of 1.0 is not more than 1.0 × 10 ²⁰ spins / cm ³ . The photoconductive member for electrophotography of the second invention of the present invention is a photoconductive layer, a surface layer, which comprises a support, silicon as a matrix, and at least one of a hydrogen atom and a halogen atom as a constituent atom. A photoreceptive layer formed on the support, and a spin concentration measured by ESR from the free surface side of the photoreceptive layer is 1.0 × 10 ²⁰ spins / cm. ³
The surface layer having a layer thickness of 20Å to 15 μm and an atom selected from boron, oxygen, nitrogen and carbon is 1 to 1 × 1.
And a photoconductive layer containing 0 ³ atomic ppm.

The photoconductive member of the present invention configured to take the layer structure as described above can solve all of the above-mentioned problems,
It exhibits extremely excellent electrical, optical, photoconductive properties and use environment properties.

In particular, when it is applied as an electrophotographic image forming member, it has an excellent charge retention ability during charging processing, there is no effect of residual potential on image formation, its electrical characteristics are stable, and it has high sensitivity. It has a high S / N ratio, high image density, clear halftone, high resolution, high quality visible image, light fatigue, repeated use characteristics, and high humidity. Good at repeated use characteristics in an atmosphere.

Hereinafter, the photoconductive member of the present invention will be described in detail with reference to the drawings.

FIG. 1 and FIG. 2 schematically show the layer structure for explaining the constitution of the photoconductive member of the present invention.

The light receiving layer 100 of the present invention has two types of layer structures. One of them is a high resistance type photoreceptive layer represented by FIG. 1, and a high resistance photoconductive layer 102 containing a-Si (H, X) as a main component is formed on a support 101. Also, a surface layer 103 containing a-Si as a main component, which is provided for the purpose of protecting the same, is formed. The other one is a charge-injection-blocking type photoreceptive layer as represented by FIG. 2, which is made of, for example, boron, oxygen, nitrogen, carbon or the like on the support 101 in order to prevent charge injection. A-Si (H, X) -containing charge injection blocking layer 104 containing at least one atom and a-Si (H, X) -containing photoconductive layer 105 are formed in the layer direction. Further, a surface layer 103 containing a-Si as a main component is formed for the purpose of protecting these layers.

Regardless of the type of layer structure, the surface layer 103 is characterized by containing silicon and atoms such as hydrogen or / and carbon, nitrogen, oxygen, etc., and the layer direction and the direction parallel to the support surface. Concentration distribution may be uniform with respect to
Alternatively, it may have a distribution such that its concentration decreases toward the support surface. The layer thickness of the surface layer 103 is preferably
1.0 × 10 ¹⁹ spins / cm ³ or less, optimally 20Å to 15 μm,
More preferably 30Å-10 μm, optimally 40Å-5
μm. The spin concentration measured by ESR of the surface layer 103 is usually 1.0 × 10 ²⁰ spins / cm ³ or less, and more preferably 1.0 × 10 ¹⁸ spins / cm ³ or less.

Further, the atoms contained for giving the photoconductive layer 102 high resistance include boron, oxygen, nitrogen, carbon, etc., and the minimum concentration of these atoms in the photoconductive layer 102 is preferably 1 ˜1 × 10 ³ atomic ppm, more preferably 50
~ 5 × 10 ² atomic ppm, optimally 100-5 × 10 ² atomic pp
It is assumed to be m. As a result, the electric resistance of the photoconductive layer 102 is
A dark resistance value of about 10 ¹² Ω ^-1 cm ^-1 or more can be obtained.

Further, the maximum concentration of boron, oxygen, nitrogen, carbon, etc. contained in the charge injection blocking layer 104 for blocking charge injection is preferably 30 to 5 × 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ⁴ atomic ppm, optimally 100
˜5 × 10 ³ atomic ppm. The charge injection blocking layer 10
The layer thickness of 4 is preferably 20 Å to 15 μm, more preferably 30 Å to 10 μm, most preferably 40 Å to 5 μm.

The photoconductive layer 105 contains a-Si (H, X) as a main component and may or may not contain an atom such as boron, oxygen, nitrogen, or carbon as the third atom. The layer thickness of the photoconductive layer 105 is preferably 1 to 100 μm, more preferably 1 to 80 μm, and most preferably 2 to 50 μm.

Thus, the photoconductive member of the present invention provided with a surface layer containing at least one atom of hydrogen, carbon, nitrogen, oxygen, etc. and having the spin concentration measured by ESR as described above is for electrophotography. When used as an imaging member,
In particular, even when the image density is high and the image exposure amount is large, image deletion does not occur, a halftone is clearly displayed, and a high-quality visible image with high resolution can be obtained for a long time. The reason for this is to protect the surface of the high-receptivity photoreceptive layer and the photoreceptive layer provided with a charge injection blocking layer from chemically or physically severe conditions such as corona charging, friction with toner and paper, or cleaning with a blade. It is presumed that the surface layer has the electrical characteristics that the durability is improved and the above-mentioned effects of the photoconductive layer are not lost.

That is, the spin concentration measured by ESR in the layer region of at least 20 Å layer thickness of the surface layer is 1 × 10 ²⁰ s
When the density is pins / cm ³ or less, dangling bonds are reduced in the molecular structure of the surface layer, so that a stable layer with low reactivity is formed, and since the stable structure is taken, hardness can be sufficiently improved. Is. Also in terms of electrical characteristics, it is possible to obtain a dark resistance value of 10 ¹⁴ Ω ⁻¹ · cm ⁻¹ , and a very good charge acceptance capability is achieved.

In the present invention, as the halogen atom (X) that may be contained in the light receiving layer, specifically, fluorine, chlorine, bromine,
Iodine can be mentioned, but chlorine and especially fluorine can be mentioned as a preferable example. Also, the surface layer 103
Examples of the atom contained in include boron, oxygen, nitrogen, carbon, and the like, with boron, particularly carbon being particularly preferable. Further, these atoms may be contained alone or in appropriate combination.

The support used in the present invention may be conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pd and alloys thereof.

As the electrically insulating support, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinyldene chloride, polystyrene or polyamide, glass, ceramic, paper or the like is usually used. . It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is provided on the surface side subjected to the conductive treatment.

That is, for example, if it is glass, NiCr, Al,
Cr, Mo, Au, Ir, Nd, Ta, V, Ti, Pt, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + SnO
₂ ) is provided with conductivity by providing a thin film, or a synthetic resin film such as a polyester film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
A thin film of a metal such as Ti or Pt is provided on the surface by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like, or the surface is laminated with the metal to impart conductivity to the surface.

The shape of the support may be determined as desired. For example, if the photoconductive member shown in FIG. 1 is used as an electrophotographic image forming member, an endless belt is used for continuous high-speed copying. It is desirable that the shape is cylindrical or cylindrical. The thickness of the support is appropriately determined so that a desired photoconductive member is formed, but when flexibility is required as the photoconductive member, the function as the support is sufficiently exerted. If it is within the range, it is made as thin as possible. However, in such a case, it is usually 10 μm or more from the viewpoints of production and handling of the support, and mechanical strength and the like.

In the present invention, in order to form the light-receiving layer composed of a-Si (H, X), a vacuum deposition method utilizing a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used. Applied.

For example, in order to form a light-receiving layer composed of a-Si (H, X) by the glow discharge method, basically, a silicon atom (Si) is used.
Hydrogen gas (H) together with the source gas for Si supply that can supply
A raw material gas for introduction and / or a raw material gas for introducing a halogen atom (X), and a raw material gas for introducing boron, oxygen, nitrogen and carbon atoms depending on the constituent atomic composition of the forming region are optionally selected from Ar, He, etc. Along with the inert gas, the gas is introduced into the deposition chamber where the pressure can be reduced at a predetermined mixing ratio and gas flow rate, and glow discharge is caused in the deposition chamber to create a plasma atmosphere of these gases. By forming it, a-Si (H, X) is formed on the surface of the support that has been installed in advance.
To form a layer consisting of.

Further, in the case of forming by the sputtering method, for example, A
When sputtering a target composed of Si in an atmosphere of an inert gas such as r or He or a mixed gas based on these gases, hydrogen atom (H) and / or halogen atom
(X) A gas for introduction and a source gas for introducing boron, oxygen, nitrogen and carbon atoms may be introduced into the deposition chamber for sputtering in accordance with the composition atomic composition of the formation region.

As the raw material gas for supplying Si used in the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. in a gaseous state or gasifiable hydrogen silicon (silanes) is effective. Among them, SiH ₄ and Si ₂ H ₆ are preferable because they are easy to handle in layer forming work and have good Si supply efficiency.

In order to introduce a hydrogen atom into the photoreceptor layer in the present invention,
It is carried out mainly by supplying H ₂ or a gas of silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ into the deposition chamber to cause discharge.

Effective as a source gas for introducing a halogen atom that can be used in the present invention, many halides,
Preferable examples include halogen compounds in a gas state or gasifiable such as halogen gas, halides, interhalogen compounds, and silane derivatives substituted with halogen. Furthermore, a silicon compound containing a halogen atom, which is composed of a silicon atom and a halogen atom and is in a gas state or can be gasified, can be cited as an effective one.

The halogen compounds that can be preferably used in the present invention, specifically, fluorine, chlorine, bromine, halogen gas such as _{iodine, BrF, ClF, ClF 3,} BrF 3, BrF 5, IF 3, IF 7, ICl, An interhalogen compound such as IBr can be mentioned.

Silicon compounds containing halogen atoms, so-called halogen atom-substituted silane derivatives, specifically, SiF ₄ , Si ₂
Silicon halides such as F ₆ , SiCl ₄ and SiBr ₄ can be mentioned as preferable ones.

As a raw material gas for introducing a halogen atom into the light-receiving layer, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used, but in addition, HF, HCl, HBr, HI Hydrogen halide such as SiH
_{2 F 2, SiH 2 I 2} , SiH 2 Cl 2, SiHCl 3, SiH 2 Br 3, SiHBr 3 and halogen-substituted silicon hydride may or gasification of so gaseous state, and one of the components of a hydrogen atom Halides can also be mentioned as effective starting materials for forming the light-receiving layer.

For these halides containing hydrogen atoms, a halogen atom should be introduced into the layer at the same time as the introduction of a hydrogen atom as an extremely effective component for controlling the electrical or photoelectric properties during the formation of the light-receiving layer. Therefore, it is used as a preferable raw material for introducing a halogen atom in the present invention.

The raw material gas for supplying boron atoms used in the present invention has B as a constituent atom, for example, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H
_Examples include ₉ , B ₅ H ₁₁ and B ₆ H ₁₀ .

Examples of the raw material gas for supplying oxygen atoms used in the present invention include O ₂ , NO and NO ₂ .

The raw material gas for supplying nitrogen atoms used in the present invention has N as a constituent atom, for example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), Ammonium azide (NH ₄ N ₃ ) and other gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides. In addition to this, nitrogen trifluoride (F ₃ N), since it is possible to introduce a halogen atom in addition to the introduction of a nitrogen atom,
Mention may be made of nitrogen halide compounds such as nitrogen tetrafluoride (F ₄ N ₂ ).

The raw material gas for supplying carbon atoms used in the present invention has C as a constituent atom, for example, CH ₄ , C ₂ H ₄ , C ₃ H ₈ , C ₃
H ₁₀ can be mentioned. In addition to this, in addition to the introduction of carbon atoms, the a-Si: H layer can be simultaneously deposited (C
_{H 3) SiH 3, (CH} 3) 2 SiH 2, (CH 3) 3 SiH, may be mentioned (CH ₃₎ in the gaseous state of ₄ Si, etc. or carbon silicon hydride can be gasified.

In order to form a light-receiving layer made of a-Si (H, X) by the reactive sputtering method or the ion plating method, for example, in the case of the sputtering method, a target made of Si is used. Sputtering in a gas plasma atmosphere, in the case of the ion plating method,
Polycrystalline silicon or single crystal silicon is used as an evaporation source in a vapor deposition port, and this silicon evaporation source is heated and vaporized by a resistance heating method, an electron beam method (EB method), or the like, and flying evaporates in a predetermined gas plasma atmosphere. It can be carried out by passing it.

At this time, in either case of the sputtering method or the ion braiding method, in order to introduce a predetermined atom into the layer to be formed, a hydrogen atom (H) and / or a halogen atom (X) introduction gas and Boron depending on the constituent atomic composition of the formation region,
The raw material gas for introducing oxygen, nitrogen and carbon atoms is introduced into the deposition chamber for spattering and ion plating, including an inert gas such as He and Ar if necessary, and the plasma atmosphere of the gas is introduced. It should be formed.

To control the amount of hydrogen atom, halogen atom, boron atom, oxygen atom, nitrogen atom and carbon atom contained in the light receiving layer, for example, hydrogen atom (H), halogen atom (X), boron atom (B ), Oxygen atom (O), nitrogen atom (N), the amount of the starting material used to contain the carbon atom (C) to be introduced into the deposition apparatus system, the support temperature, the discharge power, etc. You can control more than one.

In the present invention, a so-called rare gas, such as He, Ne, or Ar, can be preferably used as the dilution gas used when the light receiving layer is formed by the glow discharge method or the sputtering method.

Next, an example of a method for manufacturing a photoconductive member produced by the glow discharge decomposition method will be described.

FIG. 3 shows an apparatus for producing a photoconductive member by the glow discharge decomposition method.

In the gas cylinders 1102 to 1106 in the figure, a raw material gas for forming the light receiving layer of the photoconductive member of the present invention is sealed. For example, 1102 is SiH ₄ gas (purity 99.99). %) Cylinder, 1103 is B ₂ H diluted with H _2.
6 gas (purity 99.99%, hereinafter abbreviated as B ₂ H ₆ / H ₂ gas) cylinder, 1104 is NO gas (purity 99.99%) cylinder, 1105 is CH ₄
Gas (purity 99.99%) cylinder, 1106 is Ar gas (purity 9
It is a cylinder. Although not shown, a desired gas species can be added in addition to these, if necessary.

In order to allow these gases to flow into the reaction chamber 1101, the valves 1122 to 1126 of the gas cylinders 1102 to 1106 and the leak valve 11 are used.
Make sure that 35 is closed and that the inflow valve 11
12 to 1116, outflow valves 1117 to 1121 and auxiliary valves 1132, 1
Make sure 133 is open, first main valve 1
134 is opened and the reaction chamber 1101 and the gas pipe are exhausted. Next, when the reading of the vacuum gauge 1136 becomes about 1 × 10 ⁻⁶ torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, from the gas cylinder 1102, SiH ₄ gas, gas cylinder
1102 B ₂ H ₆ / H ₂ gas, gas cylinder 1104 NO gas, gas cylinder 1105 CH ₄ gas, gas cylinder 1106 Ar gas Open valves 1122 to 1126 respectively, outlet pressure gauge 1127
Adjust the pressure of ~ 1131 to 1kg / cm ² and inflow valve 1112 ~ 111
6 is gradually opened to flow into the mass flow controllers 1107-1111. Subsequently, the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are gradually opened to allow the respective gases to flow into the reaction chamber 1.
Inflow into 101. Adjust the outflow valves 1117 to 1121 so that the ratio of each of these gas flow rates at this time becomes a desired value,
In addition, a vacuum gauge 11 so that the pressure in the reaction chamber reaches a desired value.
Adjust the opening of the main valve 1134 while watching the 36 reading. And the temperature of the gas cylinder 1137 is the heater 11
After confirming that the temperature is set to 50 to 400 ° C. by 38, the power source 1140 is set to a desired electric power to cause glow discharge in the reaction chamber 1101.

At the same time, in order to obtain the previously designed boron atom and oxygen atom contents, the B ₂ H ₆ / H ₂ gas and NO gas flow rates are appropriately changed, and it is necessary to correct the plasma state that changes accordingly. Accordingly, the discharge power, the substrate temperature, etc. are controlled to form the photoconductive layer 102.

Further, during the layer formation, the base cylinder 1137 is rotated at a constant speed by the motor 1139 in order to make the layer formation uniform.

Next, close all the gas operation valves used and
Evacuate 1101 once. Reading of vacuum gauge 1136 is about 1 × 10
When it becomes ^-6 torr, the outflow valve 1121 and the correction valve 11
33 is gradually opened to allow Ar gas to flow into the reaction chamber 1101. At this time, the flow rate of Ar gas should be adjusted so that the flow rate of Ar gas becomes a desired value.
1121 is adjusted, and the opening of the main valve 1134 is adjusted while observing the reading of the vacuum gauge 1136 so that the pressure in the reaction chamber becomes a desired value. Next, the power supply 1145 is set to a desired power to generate Ar ion bombardment in the reaction chamber 1101. As a result, the surface of the photoconductive layer 102 formed by the above method and the inner surface of the reaction chamber 1101 are cleaned.

Next, close all the gas operation valves used and
Evacuate 1101 once. At this time, the shutter 1143 on the deposited glass sampling quartz glass 1142 set on the dummy cylinder 1141 placed on the base cylinder 1137 is opened by the electromagnetic switch 1144. When the reading of the vacuum gauge 1136 is about 1 × 10 ⁻⁶ torr, repeat the same operation as above, open the operation system valves for SiH ₄ and CH ₄ , and set the flow rate of each source gas to the desired value. The surface layer 10 is adjusted to produce a glow discharge in the same manner as above.
Forming 3

Examples will be described below.

Example 1 Using the photoconductive member manufacturing apparatus shown in FIG. 3, the first step was performed on the cylinder made of Al by the glow discharge decomposition method described in detail above.
A light-receiving layer was formed according to the production conditions shown in the table. The spin concentration of the obtained a-SiC layer on the deposited film sampling quartz glass 1142 was quantified using ESR, and the results shown in Table 2 were obtained. Also, the obtained photoconductive member is set in an electrophotographic apparatus and charged with a corona voltage of +6 KV and an image exposure of 0.8 to 1.5.
A latent image was formed by lux · sec, and subsequently, each process of development, transfer and fixing was carried out by a known method, and image evaluation was carried out. For image evaluation, A4 size paper was used in a normal environment, a total of 800,000 images were printed, and 150,000 images were printed in a high-temperature and high-humidity environment. Each sample was evaluated for superiority or inferiority such as [density] [resolution] [gradation reproducibility] [image defect], etc., but extremely good evaluation was obtained for all of the above items regardless of environmental conditions and durability. Was obtained. In particular, there is something to be noted about the item of [density], and it was confirmed that an extremely high light density was obtained. This is also confirmed by the result of the potential measurement, and it was found that the receptive potential was improved by about 1.2 to 1.5 times as compared with, for example, one in which the surface of the photoconductive layer was not treated. This improvement in the charge-accepting ability is not limited to only the image density, but has a great advantage that a latitude of a wide corona condition can be obtained and the selection range of the image quality is expanded.

[Resolution] is mentioned as a further noteworthy item, and it was found in this series of tests that an extremely clear image can be maintained under any environmental conditions.

These high-durability and high-quality images are considered to be the effect of providing the a-SiC layer having a low spin concentration measured by ESR on the free surface side of the light-receiving layer, and such an a-SiC layer is not provided. There was a marked difference from the one under normal environment and high temperature condition.

Example 2 and Comparative Example 1 A drum-shaped photoconductive member was produced in the same manner as in Example 1 except that the manufacturing conditions of the surface layer 103 in Example 1 were changed to those shown in Table 3. did. When this photoconductive member was evaluated for durability and image in the same manner as in Example 1, the results shown in Table 4 were obtained.

Example 3 A drum-shaped photoconductive member was produced in the same manner as in Example 1 under the production conditions shown in Table 5. The spin concentration measured by ESR of a-SiC forming the surface layer of the obtained drum-shaped photoconductive member was quantified as shown in Table 6. When this photoconductive member was evaluated for durability and images in exactly the same manner as in Example 1, good results almost equivalent to those in Example 1 were obtained.

[Brief description of drawings]

1 and 2 are schematic diagrams for explaining the layer structure of the photoconductive member of the present invention. FIG. 3 is a view showing an apparatus for manufacturing a photoconductive member by the glow discharge decomposition method. 100 ... Photoreceptive layer 101 ... Support 102 ... Photoconductive layer 103 ... Surface layer 104 ... Charge injection blocking layer 105 ... Photoconductive layer 1101 ... Reaction chamber 1102-1106 ... Gas cylinder 1122-1126 ... … Valves 1107 to 1111 …… Mass flow controller 1127 to 1131 …… Pressure regulator 1112 to 1116 …… Inflow valve 1117 to 1121 …… Outflow valve 1132 …… Auxiliary valve 1133 …… Main valve 1134 …… Gate valve 1135 …… Leak valve 1136 …… Vacuum gauge 1137 …… Base cylinder 1138 …… Heater 1139 …… Motor 1140 …… High frequency power source (matching box) 1141 …… Dummy cylinder 1142 …… Quartz glass for sampling deposition film 1143 …… Shutter 1144 ...... Electromagnetic switch 1145 ...... High voltage DC power supply

Claims (2)

[Claims] 1. A light comprising a support, and a photoconductive layer and a surface layer which are composed of silicon as a base material and contain at least one of a hydrogen atom and a halogen atom as a constituent atom on the support. In a photoconductive member for electrophotography having a receptive layer, the spin concentration measured by ESR in the surface layer region at a layer thickness of at least 20Å from the free surface side of the photoreceptive layer is 1.0 × 10 ²⁰ spins / cm ³ A photoconductive member for electrophotography, comprising: 2. A light comprising a support, a photoconductive layer and a surface layer, which are composed of silicon as a base material and contain at least one of a hydrogen atom and a halogen atom as a constituent atom, on the support. In a photoconductive member for electrophotography having a receptive layer, the spin concentration measured by ESR from the free surface side of the photoreceptive layer is 1.0 × 10 ²⁰ spins / cm ³ or less and the layer thickness is 20Å to 15 μm. The surface layer and atoms selected from boron, oxygen, nitrogen and carbon are 1 to 1 × 10 ³ atomic ppm
A photoconductive member for electrophotography, comprising a photoconductive layer containing the same.